CN115414910B - Preparation method of magnetic porous biological carbon material - Google Patents

Preparation method of magnetic porous biological carbon material Download PDF

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CN115414910B
CN115414910B CN202210918762.4A CN202210918762A CN115414910B CN 115414910 B CN115414910 B CN 115414910B CN 202210918762 A CN202210918762 A CN 202210918762A CN 115414910 B CN115414910 B CN 115414910B
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hydrothermal
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CN115414910A (en
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费会
高树民
江海婷
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Wuhan Polytechnic University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton

Abstract

The invention discloses a preparation method of a magnetic porous biological carbon material, which comprises the following steps: washing, peeling, airing and shearing biomass to prepare powder, and then mixing the powder with a salt solution to obtain a mixed solution; heating the mixed solution to perform a hydrothermal reaction, collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain hydrothermal carbon; uniformly mixing hydrothermal carbon, molten salt and ferric salt to obtain a mixture, heating the mixture to carbonize under the environment of isolating oxygen, cooling, and then washing and drying carbonized products to obtain carbide; and heating and activating the carbide in a water vapor environment, and cooling to obtain the magnetic porous biological carbon material. The magnetic porous biochar material prepared by the invention has the characteristics of large specific surface area and regular structure, has higher adsorption capacity, and solves the problem of poor adsorption performance caused by hard control of the biochar morphology and structure due to the internal tissue of the precursor.

Description

Preparation method of magnetic porous biological carbon material
Technical Field
The invention relates to the technical field of adsorption material preparation, in particular to a preparation method of a magnetic porous biological carbon material.
Background
At present, a large amount of industrial wastewater is discharged, for example, many dyes in dye wastewater have a certain harm to the environment and human body health, so that the removal of organic dyes from the industrial wastewater is very important. The magnetic porous carbon material has the characteristics of high specific surface area, high pore volume, strong adsorption capacity, magnetic separability and the like, and has great application potential in the fields of dye wastewater treatment, purification and the like.
Lignocellulose such as straw, leaves, wood chips and the like is the most abundant biomass resource on the earth, and has a very firm network-shaped organization structure. Because the firm net structure can be inherited, lignocellulose is used as a carbon source, and the porous carbon material can be conveniently prepared through the processes of pyrolysis, hydrothermal carbonization and the like, and the cost is low. However, the prepared carbon material is limited by a firm network structure of a precursor thereof, the morphology structure is difficult to control, the pore size distribution is wide, pore channels are randomly connected, the adsorption performance and the ion transmission performance are poor, and the application of the carbon material in various fields is limited.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a magnetic porous biological carbon material, aiming at improving the adsorption performance of the biological carbon material.
In order to achieve the above object, the present invention provides a method for preparing a magnetic porous biochar material, comprising the steps of:
washing, peeling, airing and shearing biomass to prepare powder, and then mixing the powder with a salt solution to obtain a mixed solution;
heating the mixed solution to perform a hydrothermal reaction, collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain hydrothermal carbon;
uniformly mixing the hydrothermal carbon, molten salt and ferric salt to obtain a mixture, heating the mixture to carbonize under the environment of isolating oxygen, cooling, and then washing and drying carbonized products to obtain carbide;
and heating and activating the carbide in a water vapor environment, and cooling to obtain the magnetic porous biochar material.
Optionally, the steps of washing, peeling, airing and shearing biomass to prepare powder, and then mixing the powder with a salt solution to obtain a mixed solution include:
the biomass comprises at least one of corn stover, soybean stover, and wood chips.
Optionally, the steps of washing, peeling, airing and shearing biomass to prepare powder, and then mixing the powder with a salt solution to obtain a mixed solution include:
the salt solution comprises at least one of potassium chloride solution, sodium sulfate solution and sodium chloride solution; and/or the number of the groups of groups,
the molar concentration of the salt solution is 0.05-0.2 mol/L.
Optionally, the steps of washing, peeling, airing and shearing biomass to prepare powder, and then mixing the powder with a salt solution to obtain a mixed solution include:
the mass ratio of the biomass to the salt solution is 1: (50-200).
Optionally, heating the mixed solution to perform a hydrothermal reaction, collecting a solid product generated by the hydrothermal reaction, and washing and drying to obtain the hydrothermal carbon:
the reaction temperature of the hydrothermal reaction is 80-160 ℃ and the reaction time is 6-12 h.
Optionally, uniformly mixing the hydrothermal carbon, molten salt and ferric salt to obtain a mixture, heating the mixture to carbonize in an oxygen-isolated environment, cooling, and then washing and drying the carbonized product to obtain carbide:
the fused salt comprises LiCl/KCl system fused salt, naCl/KCl system fused salt and ZnCl 2 At least one of the fused salts of the KCl system; and/or the number of the groups of groups,
the iron salt comprises Fe 2 (SO 4 ) 3 、FeCl 3 、Fe 2 (NO 3 ) 3 At least one of (a) and (b); and/or the number of the groups of groups,
the mass ratio of the hydrothermal carbon, the molten salt and the ferric salt is (0.5-2): (20-50): (0.05-0.2).
Optionally, uniformly mixing the hydrothermal carbon, molten salt and ferric salt to obtain a mixture, heating the mixture to carbonize in an oxygen-isolated environment, cooling, and then washing and drying a carbonized product to obtain carbide, wherein the method comprises the following steps of:
ball-milling the mixture of the hydrothermal carbon, the molten salt and the ferric salt uniformly to obtain a mixture;
heating the mixture to 200-400 ℃ at a heating rate of 1-5 ℃/min under nitrogen atmosphere, preserving heat for 1-3 h, heating to 600-1100 ℃ and preserving heat for 1-3 h, naturally cooling to room temperature under nitrogen atmosphere, and washing and drying the carbonized product to obtain carbide.
Optionally, the step of washing the carbonized product comprises:
adding hydrochloric acid solution into carbonized product, stirring at room temperature for 12-24 hr, collecting precipitate, washing the precipitate with distilled water.
Alternatively, a hydrochloric acid solution is added to the carbonized product, and then stirred at room temperature for 12 to 24 hours, and a precipitate is collected, and washed with distilled water in the step of:
the mass concentration of the hydrochloric acid solution is 10-30%, and the mass ratio of the carbonized product to the hydrochloric acid solution is 1: (100-200).
Optionally, the carbide is heated and activated in a water vapor environment, and the step of cooling to obtain the magnetic porous biological carbon material comprises the following steps:
heating the carbide to 600-1100 ℃ at a heating rate of 1-5 ℃/min in a water vapor atmosphere, preserving heat for 1-3 h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
In the technical scheme provided by the invention, biomass is taken as a raw material, and hydrothermal reaction is carried out firstly to disperse internal tissues of the biomass into a plurality of small fragments; then, mixing the carbide powder with molten salt and ferric salt, carbonizing at high temperature, and regulating and controlling the morphology structure of the product by taking molten salt ions as templates to obtain the carbide embedded by the iron species with regular structure; and then carrying out steam activation on carbide, and carrying out steam oxidation on the embedded iron species to become magnetic ferroferric oxide by exposing the embedded iron species during pore-forming through a water-carbon reaction to prepare the magnetic porous biological carbon material. Therefore, the prepared magnetic porous biochar material has the characteristics of large specific surface area and regular structure, has higher adsorption capacity, and well solves the problem of poor adsorption performance caused by hard control of the biochar morphology structure due to the internal tissue of the precursor.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other related drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of an embodiment of a method for preparing a magnetic porous biochar material according to the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The lignocellulose is used as a carbon source, and porous carbon materials can be conveniently prepared through pyrolysis, hydrothermal carbonization and other processes, and the cost is low, however, the prepared carbon materials are limited by a firm reticular structure of a precursor, the morphology structure is difficult to control, the pore size distribution is wide, pore channels are randomly connected, the adsorption performance and the ion transmission performance are poor, and the application of the porous carbon materials in various fields is limited.
In order to solve the problems of poor adsorption performance and the like caused by the fact that the morphology structure of the biological carbon material is limited by the tissue structure of the precursor, the invention provides a preparation method of a magnetic porous biological carbon material, and fig. 1 shows an embodiment of the preparation method of the magnetic porous biological carbon material. Referring to fig. 1, in this embodiment, the preparation method of the magnetic porous biochar material includes the following steps:
step S10, cleaning, peeling, airing and shearing biomass to prepare powder, and then mixing the powder with a salt solution to obtain a mixed solution;
step S20, heating the mixed solution to perform a hydrothermal reaction, collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain hydrothermal carbon;
step S30, uniformly mixing the hydrothermal carbon, molten salt and ferric salt to obtain a mixture, heating the mixture to carbonize in an oxygen-isolated environment, cooling, and then washing and drying a carbonized product to obtain carbide;
and S40, heating and activating the carbide in a water vapor environment, and cooling to obtain the magnetic porous biochar material.
In the technical scheme provided by the invention, biomass is taken as a raw material, firstly washed, peeled and dried to prepare powder, and then mixed with salt solution for hydrothermal reaction to disperse internal tissues of the biomass into a plurality of small fragments; then, mixing the carbide powder with molten salt and ferric salt, carbonizing at high temperature, and regulating and controlling the morphology structure of the product by taking molten salt ions as templates to obtain the carbide embedded by the iron species with regular structure; and then carrying out steam activation on carbide, and carrying out steam oxidation on the embedded iron species to become magnetic ferroferric oxide by exposing the embedded iron species during pore-forming through a water-carbon reaction to prepare the magnetic porous biological carbon material. Therefore, the prepared magnetic porous biochar material has the characteristics of large specific surface area and regular structure, has higher adsorption capacity, and well solves the problem of poor adsorption performance caused by hard control of the biochar morphology structure due to the internal tissue of the precursor.
The biomass is used for providing a carbon source for the magnetic porous biochar material, any lignocellulose biomass containing carbon elements can be selected, and in the embodiment of the invention, at least one of corn straw, soybean straw and wood dust is preferably selected, either one of the biomass can be selected, and a combination of any two or three of the biomass can be selected at the same time, so that the magnetic porous biochar material belongs to the protection scope of the invention. In a preferred embodiment of the present invention, the biomass may be any one of the above biomass, which is beneficial to simplifying the process.
The salt solution is used for penetrating into the internal tissue structure of the biomass and destroying the high-energy ions of the tissue structure in the hydrothermal reaction process, and can be any solution containing salt substances of potassium element or sodium element, preferably at least one of potassium chloride solution, sodium sulfate solution and sodium chloride solution, and can be any one of the salt solutions or a mixed solution of any two or three of the salt solutions, and the salt solution belongs to the protection scope of the invention. In a preferred embodiment of the present invention, the salt solution is any one of the salt solutions.
Further, in some embodiments of the invention, the salt solution has a molar concentration of 0.05 to 0.2mol/L.
Still further, in some embodiments of the invention, the mass ratio of the biomass to the salt solution is 1: (50-200), the magnetic porous biological carbon material prepared in the range has better adsorption performance.
Lignocellulose is the most abundant biomass resource on earth, such as agricultural wastes of straws, stalks and the like, and a large amount of agricultural waste biomass of straws, stalks and the like is produced annually in China, so that the environment is greatly destroyed by incineration treatment, and the biomass resource is wasted. The carbon material is prepared from agricultural waste biomass, and is applied to the fields of sewage treatment and energy storage, so that the environmental pollution problem can be effectively relieved, and considerable economic benefits can be brought. However, lignocellulose is a very strong network of cellulose-hemicellulose-lignin, and is resistant to biological or non-biological attack in the environment. Therefore, lignocellulose-based porous carbon is limited by the firm tissue structure of the precursor, and the morphology and structure of the lignocellulose-based porous carbon are not easy to control.
In order to obtain the desired biochar, it is necessary to destroy the firm structure of the precursor, and methods such as pyrolysis and hydrothermal methods are used. The hydrothermal method can avoid the defects of volatilization of reactants, stress induction defect, mutual reaction of phases and the like at high temperature, and more importantly, the shape, the size, the viscosity distribution and the like of the product can be controlled by adjusting the reaction conditions. In the embodiment of the invention, an inorganic auxiliary hydrothermal method is adopted, the reaction temperature of the hydrothermal reaction is controlled to be 80-160 ℃ and the reaction time is controlled to be 6-12 hours, so that the lignocellulose tissue structure is decomposed into a plurality of uniform small fragments, and conditions are provided for the formation and activation of a carbon matrix with a regular structure.
The synthesis method of the magnetic porous carbon material mainly comprises a hydrothermal method, a molten salt synthesis method, a coprecipitation method and a direct carbonization metal organic framework material method. The molten salt synthesis method uses molten salt as a template, so that the morphology and structure of the product can be reconstructed, and the magnetic porous carbon material with rich pore channels can be easily obtained. Specifically, in the embodiment of the invention, the hydrothermal carbon is used as a carbon source, the ferric salt is used as an iron source, and the iron-embedded carbide is prepared by adopting a molten salt synthesis method under the condition of isolating oxygen. The oxygen-isolated environment may be achieved by filling inert gas such as nitrogen, argon, etc., and the oxygen-isolated environment is described below by taking the example of filling nitrogen, the specific steps of the molten salt synthesis method include:
step S31, ball milling the mixture of the hydrothermal carbon, the molten salt and the ferric salt uniformly to obtain a mixture;
and step S32, heating the mixture to 200-400 ℃ at a heating rate of 1-5 ℃/min under nitrogen atmosphere, preserving heat for 1-3 h, heating to 600-1100 ℃ and preserving heat for 1-3 h, naturally cooling to room temperature under nitrogen atmosphere, and washing and drying the carbonized product to obtain the carbide.
Firstly heating the mixture to 200-400 ℃, and preserving heat for 1-3 hours, so that the hydrothermal carbon, molten salt and ferric salt can be fully melted and effectively dissolved, and molten salt and ferric salt molecules can effectively permeate and diffuse into the internal tissues of the hydrothermal carbon and are fully mixed with the internal structural units of the hydrothermal carbon; the mixture is further heated to 500-900 ℃ and is kept for 1-3 hours, hydrothermal carbon is further graphitized, carbon is transited from an sp3 hybridization state to an sp2 hybridization state, carbonized products with lamellar structures are generated in the process, and meanwhile, high-temperature molten salt is continuously permeated and is finally embedded in a carbon material matrix to prevent carbon sheets from being stacked, so that the products keep the lamellar structures; meanwhile, high-energy ions in the molten salt can further etch the carbon sheet to form a large number of microporous pore structures: on the other hand, the iron salt permeated into the hydrothermal carbon is carbothermally reduced to catalyze the carbon matrix, catalyze the graphitized carbon coating layer, and finally uniformly embed into the carbon matrix. When the temperature of the system is reduced below the melting point of the salt, the molten salt will recrystallize and a large portion of the salt particles will intercalate into the carbon product matrix to act as templates, and when these salt particles are separated from the product, abundant macropores or mesopores will remain in the carbon product, forming hierarchical pore structure carbon nanoplatelets in which iron species are homogeneously intercalated.
And after the carbonization reaction is finished, removing molten salt templates in the carbonized solid product to obtain the indicated iron species, thereby obtaining the target product. In the embodiment of the invention, the method is realized by adding an acidic solution into the carbonized solid product, and specifically comprises the following steps: adding hydrochloric acid solution into carbonized product, stirring at room temperature for 12-24 hr to eliminate molten salt template and iron species on the surface, separating and collecting precipitate, washing the precipitate with distilled water and drying to obtain carbide embedded with iron species.
Further, in some embodiments of the present invention, the mass concentration of the hydrochloric acid solution is 10 to 30%, and the mass ratio of the carbonized product to the hydrochloric acid solution is 1: (100-200).
The ferric salt is used for providing an iron source for the magnetic porous biochar material, and any inorganic salt substance containing iron element can be selected, and preferably comprises Fe in the embodiment of the invention 2 (SO 4 ) 3 、FeCl 3 、Fe 2 (NO 3 ) 3 At least one of them can be eitherAny one of the above iron salts, or a mixture of any two or more thereof, falls within the scope of the present invention. In a preferred embodiment of the present invention, any one of the above-mentioned iron salts may be used.
The molten salt is short for melting inorganic compound, and is used as solvent, reaction medium and template in the molten salt synthesis process. In the whole molten salt synthesis process, molten salt undergoes the processes of melting, ionization, solidification and the like; after molten salt is melted, the liquid environment provided by the molten salt enhances the diffusion and convective mass transfer of reaction components, so that the precursor is highly dispersed; the ionized anions and cations have strong polarization force at high temperature, can be effectively adsorbed or penetrated among the generated product particles, and can effectively prevent agglomeration among the particles; finally, the fused salt is condensed into crystals, so that shrinkage and collapse of the porous carbon material can be avoided.
The choice of the molten salt is important, and due to the nature of the molten salt, molten salt synthesis is generally carried out at the melting point (T m ) And boiling point (T) b ) And at a temperature in between. T of most salts m Is a constant value, and the melting point of a binary eutectic mixture complex salt system is typically much lower than that of a single component, so multicomponent salts are typically used as molten salt systems. In addition, salts have different crystal structures, such as LiCl, naCl, and KCl are ionic compounds, with similar cubic crystal structures. In the embodiment of the invention, the molten salt preferably comprises LiCl/KCl system molten salt, naCl/KCl system molten salt and ZnCl 2 At least one of the fused salts of the KCl system can be any one of the fused salts, or can be a mixture of any two or three of the fused salts, and the fused salts belong to the protection scope of the invention. In a preferred embodiment of the present invention, the molten salt may be any one of the above molten salts.
Further, in some embodiments of the invention, the mass ratio of the hydrothermal carbon, molten salt and iron salt is (0.5-2): (20-50): (0.05-0.2).
After the carbide is prepared through carbonization reaction, the carbide needs to be activated by water vapor, and the embedded iron species are exposed and oxidized into magnetic ferroferric oxide by the water vapor to prepare the magnetic porous biological carbon material through water-carbon reaction while pore formation. Specifically, in the embodiment of the invention, the specific steps of performing steam activation on carbide are as follows: heating the carbide to 600-1100 ℃ at a heating rate of 1-5 ℃/min in a water vapor atmosphere, preserving heat for 1-3 h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
The method provided by the invention takes biomass as a carbon source, firstly carries out hydrothermal treatment, and utilizes a salt solution to permeate into the internal tissue structure of the biomass in the hydrothermal reaction process and destroy high-energy ions of the tissue structure of the biomass so as to disperse the internal tissue of the biomass into a plurality of small carbon blocks; then mixing the small carbon blocks with molten salt and ferric salt, synthesizing the mixture by using the molten salt, and reconstructing the morphology and structure of a plurality of small carbon blocks by using molten salt ions as templates to obtain iron species embedded carbide with regular structure; and activating the carbide by water vapor, and carrying out water-carbon reaction to expose and oxidize the embedded iron species into magnetic ferroferric oxide during pore-forming to prepare the magnetic porous biochar material. The prepared magnetic porous biochar material has large specific surface area and regular structure, has higher adsorption performance, and solves the problem that the morphology and structure of the biochar are difficult to control due to the internal tissue of the precursor. On the other hand, the preparation process comprises the steps of decomposing biomass into a plurality of small carbon blocks, reconstructing the morphology structure of the small carbon blocks, embedding iron species, and oxidizing the embedded iron species into magnetic ferroferric oxide to prepare a magnetic porous biochar material; the process is simple, the equipment used in the preparation process is common equipment, the price is low, the used reagents and solvents are raw materials which are wide in sources, low in price and small in environmental pollution, and the production cost of the magnetic porous biochar material is reduced.
The magnetic porous biological carbon material prepared by the method provided by the invention is detected by a transmission electron microscope, the material consists of a large number of nano sheets with regular structures, and a large number of micropores and mesopores are formed in the sheets; atomic force microscopy revealed that the thickness of the nanoplatelets was about 15.6nm; atomsAnd (3) performing element analysis on the prepared magnetic porous biological carbon material by an emission spectrometry and an element analyzer, wherein the analysis result shows that the material contains carbon element, iron element and oxygen element, and the contents of the carbon element, the iron element and the oxygen element are respectively 80.46-89.31%, 6.85-11.58% and 1.51-3.21%. N of material 2 The adsorption and desorption tests show that the specific surface area and the corresponding pore volume of the material are 1325.2m respectively 2 g -1 And 0.852cm 3 g -1 And a distinct distribution peak appears in both the micropore range of 0 to 2nm and the mesopore range of 2 to 50 nm. Further, XRD detection shows that characteristic diffraction peaks of (002) and (100) crystal faces of graphite appear at about 23.6 degrees and 45.2 degrees except for characteristic diffraction peaks of amorphous carbon, which indicates that the material is a partially graphitized polycrystalline structure; and no characteristic diffraction peak related to iron element is generated, which is probably that iron species are embedded into the carbon matrix or the mass is too little, so that no characteristic diffraction peak of iron simple substance or oxide is generated. The magnetic property detection shows that the saturation magnetization of the material is 56.2emu/g, and the material has superparamagnetism, so that the material can be rapidly recycled from water environment under the action of an external magnetic field.
The following technical solutions of the present invention will be described in further detail with reference to specific examples and drawings, and it should be understood that the following examples are only for explaining the present invention and are not intended to limit the present invention.
Example 1
(1) Cleaning corn stalks, peeling, airing, shearing, mechanically ball-milling to prepare powder, and mixing the powder with a potassium chloride solution with the concentration of 0.05mol/L according to the ratio of 1:50 mass ratio to obtain a mixed solution.
(2) And (3) heating the mixed solution prepared in the step (1) to 80 ℃ for hydrothermal reaction for 12 hours, separating and collecting a solid product generated by the hydrothermal reaction, and washing and drying to obtain the hydrothermal carbon.
(3) Molten salt of hydrothermal carbon, liCl/KCl system and Fe prepared in the step (2) 2 (SO 4 ) 3 According to 0.5:20: ball milling and mixing uniformly in a mass ratio of 0.05 to obtain a mixture; heating the obtained mixture to 200deg.C at a heating rate of 1deg.C/minHeating to 600 ℃ for 3h, preserving heat for 3h, and naturally cooling to room temperature in nitrogen atmosphere to obtain a carbonized product; the mass ratio of the carbonized product to the hydrochloric acid solution is 1:100, adding hydrochloric acid solution with the mass concentration of 10% into carbonized products, stirring for 12 hours at room temperature, washing with distilled water, and drying to obtain carbide.
(4) And (3) heating the carbide prepared in the step (3) to 600 ℃ at a heating rate of 1 ℃/min in a water vapor atmosphere, preserving heat for 3 hours to activate, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
Example 2
(1) Cleaning corn stalks, peeling, airing, shearing, mechanically ball-milling to prepare powder, and mixing the powder with a potassium chloride solution with the concentration of 0.08mol/L according to the ratio of 1:100 mass ratio to obtain a mixed solution.
(2) And (3) heating the mixed solution prepared in the step (1) to 100 ℃ for hydrothermal reaction for 10 hours, separating and collecting a solid product generated by the hydrothermal reaction, and washing and drying to obtain the hydrothermal carbon.
(3) Molten salt of hydrothermal carbon, liCl/KCl system and Fe prepared in the step (2) 2 (SO 4 ) 3 According to 1:30: ball milling and mixing uniformly in a mass ratio of 0.1 to obtain a mixture; heating the obtained mixture to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, heating to 700 ℃ again, preserving heat for 2 hours, and naturally cooling to room temperature in a nitrogen atmosphere to obtain a carbonized product; the mass ratio of the carbonized product to the hydrochloric acid solution is 1:120, adding hydrochloric acid solution with the mass concentration of 15% into carbonized products, stirring for 15 hours at room temperature, washing with distilled water, and drying to obtain carbide.
(4) And (3) heating the carbide prepared in the step (3) to 700 ℃ at a heating rate of 2 ℃/min in a water vapor atmosphere, preserving heat for 2 hours to activate, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
Example 3
(1) Cleaning soybean straw, peeling, airing, shearing, mechanically ball-milling to prepare powder, and mixing the powder with a potassium chloride solution with the concentration of 0.12mol/L according to the proportion of 1:150, and mixing the mixture to obtain a mixed solution.
(2) And (3) heating the mixed solution prepared in the step (1) to 120 ℃ for hydrothermal reaction for 8 hours, separating and collecting a solid product generated by the hydrothermal reaction, and washing and drying to obtain the hydrothermal carbon.
(3) Molten salt of hydrothermal carbon, naCl/KCl system and FeCl prepared in the step (2) 3 According to 2:40: ball milling and mixing uniformly in a mass ratio of 0.15 to obtain a mixture; heating the obtained mixture to 300 ℃ at a heating rate of 3 ℃/min, preserving heat for 2 hours, heating to 800 ℃ and preserving heat for 2 hours, and naturally cooling to room temperature in a nitrogen atmosphere to obtain a carbonized product; the mass ratio of the carbonized product to the hydrochloric acid solution is 1:200, adding hydrochloric acid solution with the mass concentration of 20% into carbonized products, stirring for 18 hours at room temperature, washing with distilled water, and drying to obtain carbide.
(4) And (3) heating the carbide prepared in the step (3) to 800 ℃ at a heating rate of 3 ℃/min in a water vapor atmosphere, preserving heat for 2 hours to activate, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
Example 4
(1) Cleaning soybean straw, peeling, airing, shearing, mechanically ball-milling to prepare powder, and mixing the powder with a potassium chloride solution with the concentration of 0.15mol/L according to the proportion of 1:80 mass ratio to obtain a mixed solution.
(2) And (3) heating the mixed solution prepared in the step (1) to 140 ℃ for hydrothermal reaction for 6 hours, separating and collecting a solid product generated by the hydrothermal reaction, and washing and drying to obtain the hydrothermal carbon.
(3) Molten salt of hydrothermal carbon, naCl/KCl system and FeCl prepared in the step (2) 3 According to 0.8:50: ball milling and mixing uniformly in a mass ratio of 0.18 to obtain a mixture; heating the obtained mixture to 350 ℃ at a heating rate of 4 ℃/min, preserving heat for 3 hours, heating to 900 ℃ and preserving heat for 1 hour, and naturally cooling to room temperature in a nitrogen atmosphere to obtain a carbonized product; the mass ratio of the carbonized product to the hydrochloric acid solution is 1:150, adding 25% of the mass concentration to the carbonized productStirring for 20h at room temperature, then washing with distilled water, and drying to obtain carbide.
(4) And (3) heating the carbide prepared in the step (3) to 900 ℃ at a heating rate of 4 ℃/min in a water vapor atmosphere, preserving heat for 2 hours to activate, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
Example 5
(1) Cleaning wood chips, peeling, airing, shearing, mechanically ball-milling to prepare powder, and mixing the powder with a potassium chloride solution with the concentration of 0.18mol/L according to the following ratio of 1:120, and obtaining a mixed solution.
(2) And (3) heating the mixed solution prepared in the step (1) to 150 ℃ for hydrothermal reaction for 8 hours, separating and collecting a solid product generated by the hydrothermal reaction, and washing and drying to obtain the hydrothermal carbon.
(3) The hydrothermal carbon and ZnCl prepared in the step (2) are treated 2 Fused salt of KCl system, fe 2 (NO 3 ) 3 According to 1.2:35: ball milling and mixing uniformly in a mass ratio of 0.2 to obtain a mixture; heating the obtained mixture to 400 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, heating to 1000 ℃ and preserving heat for 2h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain a carbonized product; the mass ratio of the carbonized product to the hydrochloric acid solution is 1:180, adding 30% hydrochloric acid solution into carbonized product, stirring at room temperature for 24h, washing with distilled water, and drying to obtain carbide.
(4) And (3) heating the carbide prepared in the step (3) to 1000 ℃ at a heating rate of 5 ℃/min in a water vapor atmosphere, preserving heat for 1h to activate, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
Example 6
(1) Cleaning wood chips, peeling, airing, shearing, mechanically ball-milling to prepare powder, and mixing the powder with a potassium chloride solution with the concentration of 0.2mol/L according to the following ratio of 1:180, and obtaining a mixed solution.
(2) And (3) heating the mixed solution prepared in the step (1) to 160 ℃ for hydrothermal reaction for 6 hours, separating and collecting a solid product generated by the hydrothermal reaction, and washing and drying to obtain the hydrothermal carbon.
(3) The hydrothermal carbon and ZnCl prepared in the step (2) are treated 2 Fused salt of KCl system, fe 2 (NO 3 ) 3 According to 1.8:45: ball milling and mixing uniformly in a mass ratio of 0.12 to obtain a mixture; heating the obtained mixture to 300 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating to 1100 ℃ and preserving heat for 1h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain a carbonized product; the mass ratio of the carbonized product to the hydrochloric acid solution is 1:130, adding hydrochloric acid solution with the mass concentration of 20% into carbonized products, stirring for 22 hours at room temperature, washing with distilled water, and drying to obtain carbide.
(4) And (3) heating the carbide prepared in the step (3) to 1100 ℃ at a heating rate of 3 ℃/min in a water vapor atmosphere, preserving heat for 2 hours to activate, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
The adsorption properties of the magnetic porous biochar materials prepared in examples 1 to 6 were analyzed, and the method and results were as follows:
the adsorption performance evaluation method comprises the following steps: the magnetic porous biochar materials prepared in the comparative examples and the above examples 1 to 6 were placed in an adsorption reaction apparatus under normal temperature and neutral conditions, respectively, and adsorption performance was evaluated by examining the purification treatment effects of different materials for dye wastewater containing malachite green, industrial wastewater of phenol and sulfaantibiotic wastewater within 2 hours, and using the removal rate of malachite green as an evaluation index.
Adsorption performance stability evaluation method: after the adsorption performance of the material is evaluated, the obtained solid material is washed and dried through centrifugal separation or filtration, and then the adsorption activity stability of the material is inspected according to the adsorption performance evaluation method.
The results of evaluation of the adsorption performance and the adsorption activity stability are shown in table 1 below.
Table 1 adsorption performance and adsorption performance stability evaluation results of examples and comparative examples
As shown by the test results in the table 1, compared with the commercial porous biochar, the magnetic porous biochar material prepared by the embodiment of the invention has obviously improved adsorption effect and stability, and the preparation method of the magnetic porous biochar material provided by the invention has the advantages that the prepared magnetic porous biochar material has large specific surface area, regular structure and higher adsorption activity through the processes of decomposition, reconstruction, activation and the like of a biomass precursor tissue structure; in addition, the iron element is distributed in the regular carbon matrix, is not easy to fall off, and can continuously and efficiently exert the adsorption effect.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The preparation method of the magnetic porous biological carbon material is characterized by comprising the following steps of:
washing, peeling, airing and shearing biomass to prepare powder, and then mixing the powder with a salt solution to obtain a mixed solution;
heating the mixed solution to perform a hydrothermal reaction, collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain hydrothermal carbon;
uniformly mixing the hydrothermal carbon, molten salt and ferric salt to obtain a mixture, heating the mixture to carbonize under the environment of isolating oxygen, cooling, and then washing and drying carbonized products to obtain carbide;
heating and activating the carbide in a steam environment, and cooling to obtain a magnetic porous biological carbon material;
wherein the salt solution comprises at least one of potassium chloride solution, sodium sulfate solution and sodium chloride solution;
the fused salt comprises LiCl/KCl system fused salt, naCl/KCl system fused salt and ZnCl 2 At least one of the fused salts of the KCl system.
2. The method for preparing a magnetic porous biochar material according to claim 1, wherein the steps of washing, peeling, air-drying, shearing biomass to obtain a powder, and mixing the powder with a salt solution to obtain a mixed solution comprise:
the biomass comprises at least one of corn stover, soybean stover, and wood chips.
3. The method for preparing a magnetic porous biochar material according to claim 1, wherein the steps of washing, peeling, air-drying, shearing biomass to obtain a powder, and mixing the powder with a salt solution to obtain a mixed solution comprise:
the molar concentration of the salt solution is 0.05-0.2 mol/L.
4. The method for preparing a magnetic porous biochar material according to claim 1, wherein the steps of washing, peeling, air-drying, shearing biomass to obtain a powder, and mixing the powder with a salt solution to obtain a mixed solution comprise:
the mass ratio of the biomass to the salt solution is 1: (50-200).
5. The method for preparing a magnetic porous biochar material according to claim 1, wherein the step of heating the mixed solution to perform a hydrothermal reaction, collecting a solid product generated by the hydrothermal reaction, and washing and drying the solid product to obtain the hydrothermal carbon comprises the steps of:
the reaction temperature of the hydrothermal reaction is 80-160 ℃ and the reaction time is 6-12 h.
6. The method for preparing a magnetic porous biochar material according to claim 1, wherein the hydrothermal carbon, molten salt and ferric salt are uniformly mixed to obtain a mixture, the mixture is heated to carbonize in an oxygen-isolated environment and then cooled, and then the carbonized product is washed and dried to obtain carbide, wherein the method comprises the steps of:
the iron salt comprises Fe 2 (SO 4 ) 3 、FeCl 3 、Fe 2 (NO 3 ) 3 At least one of (a) and (b); and/or the number of the groups of groups,
the mass ratio of the hydrothermal carbon, the molten salt and the ferric salt is (0.5-2): (20-50): (0.05-0.2).
7. The method for preparing a magnetic porous biochar material according to claim 1, wherein the steps of uniformly mixing the hydrothermal carbon, the molten salt and the iron salt to obtain a mixture, heating the mixture to carbonize in an oxygen-isolated environment, cooling, and then washing and drying the carbonized product to obtain carbide comprise the steps of:
ball-milling the mixture of the hydrothermal carbon, the molten salt and the ferric salt uniformly to obtain a mixture;
heating the mixture to 200-400 ℃ at a heating rate of 1-5 ℃/min under nitrogen atmosphere, preserving heat for 1-3 h, heating to 600-1100 ℃ and preserving heat for 1-3 h, naturally cooling to room temperature under nitrogen atmosphere, and washing and drying the carbonized product to obtain carbide.
8. The method for preparing a magnetic porous biochar material according to claim 1, wherein the step of washing the carbonized product comprises:
adding hydrochloric acid solution into carbonized product, stirring at room temperature for 12-24 hr, collecting precipitate, washing the precipitate with distilled water.
9. The method for preparing a magnetic porous biochar material according to claim 8, wherein a hydrochloric acid solution is added to the carbonized product, and then stirred at room temperature for 12 to 24 hours, and a precipitate is collected, and the precipitate is washed with distilled water in the step of:
the mass concentration of the hydrochloric acid solution is 10-30%, and the mass ratio of the carbonized product to the hydrochloric acid solution is 1: (100-200).
10. The method for preparing a magnetic porous biochar material according to claim 1, wherein the step of heating and activating the carbide in a water vapor environment and cooling the carbide to obtain the magnetic porous biochar material comprises the steps of:
heating the carbide to 600-1100 ℃ at a heating rate of 1-5 ℃/min in a water vapor atmosphere, preserving heat for 1-3 h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
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